Foil Future Fires

Readers point to possible causes of a blaze.

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We had to do a hot-tap on the top of an atmospheric tank containing crude triethylamine (boiling point: 50°C). As an extra safeguard, the approved job plan required diverting the tank's nitrogen blanket to an upper nozzle because our safety department deemed the area on top of the tank partially enclosed. Nitrogen was bubbled through a 4-ft-dia. polyethylene tank containing an aqueous 10% HCl solution; waste product overflowed the tank into a long grated drain in an area with a 6-in. dike. One side of the diked area is partially open to allow vehicle access. Plans called for scaffold erection on the first day, welding on the second day (weather-permitting) and scaffold removal on the third day. Ambient temperatures were in the mid-80°Fs. Sniff tests were performed on a periodic schedule around the work area at the top of the scaffold. A few hours into the welding, a small fire erupted several yards outside of the diked area. The safety department is investigating the accident. What do you think caused it? Is there a better way to do this welding?

I suggest limestone contacted the overflow of the polyethylene tank, neutralizing the triethylamine hydrochloride to calcium chloride and triethylamine. Triethylamine, now free to be a vapor then caused the fire. I suggest the diversion of the nitrogen blanket was an unneeded complication. Triethylamine has an upper flammable limit (UFL) of 8%. Eight percent of 760 mm Hg = 61 mm Hg. Using Antoine's equation and constants listed in Lange's, at 79°F the vapors in the tank would be above the UFL. This is a second safeguard since the tank is inert padded with nitrogen. A proper hot-tap device could also be equipped with inerting nipples, eliminating air intrusion into the tank.
Mike Gentilcore, principal research engineer
Covidien Imaging Solutions, Hazelwood, Mo.

I would guess that some triethylamine escaped from the tank and found its way into the dike. According to the MSDS I found, triethylamine is highly flammable, 3.48 times heavier than air, has a flash point of about 20°F, and an auto ignition temperature of 419°F. It's possible a spark from welding ignited the vapors if they were allowed to reach the mixture, but it could easily have ignited from any other ignition source or hot spot. With the information given, it doesn't seem that the welding itself had anything to do with the fire if it ignited several yards from the dike (assuming the ignition point was also several yards from the welding). I suspect the problem lies with improper control of the flammable material rather than the generation of an ignition source.
Pete Bisila, system reliability engineer - utilities
Flint Hills Resources, Hastings, Minn.

Sniff tests should have picked up an ignitable mixture but not if the liquid drained out of the work area. A number of questions come to mind. How was the acid concentration being maintained in the bubble column? Has this method been tested, preferably in the safety of a laboratory before risking operators? Did anyone calculate the amount of TEA potentially present in the vapor? Will a plastic tank hold up from the heat of solution with HCl-H2O and heat of reaction with TEA? Making a 10% solution of HCl by weight will produce enough heat to evaporate almost 10% of the water. Did anyone consider doing a new electrical area classification for the job plan?

Counting on operators to add acid every few hours is not a safe practice. A better approach would be to add a small acid tank and metering pump with a rheostat to adjust the flow. Inexpensive metering pumps can control to a few percent accuracy, which is more than adequate. It's crucial that the bubble column have a pH well below the pKa of the amine. Also, a cheap local pH alarm could suffice to avoid troubles. It might also be useful to establish a control link with the control room.

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